Azo-dyestuffs insoluble in water



n td W P w 2,783,225 .xzomtsiwm msowmm wArER Gerhard Langbein,Hofheim,' Taunus, Germany, assignor .to Farbwerke tHoechst Aktiengesellschaft vormals Meister Lucius &, Briining, Frankfurt am Main, Germany, a company of Germany No Drawing. Application 0ctober'27, 1953, Serial No. 388,683

Claims priority, application Germany November 3, 1952 7 Claims. 01; 260-176) The present invention relates to new azo-dyestuffs insoluble in water and to fiber dyed therewith; moreparticularly itrelates to azo-dyestufis corresponding to the following general formula of lakes a diazo-compound of an aminoazo-compound of the following general formula wherein R and R1 have the meanings given above, with an arylide of 2i3-hydroxynaphthoic acid, the dyestuif components being free from groups imparting solubility in water, such as'sulfonic acid or carboxylic acid groups.

Alarge number of the new diazo-componentsyield bluergreen to green tints which could hitherto be .obtained in practice only with the use of arylides of 2.3- hydroxyanthracene-carboxylic acid. 'Immany cases the dyestuifs of the invention possess a better fastness to light and chlorine than the knowngreen dyestuffs which are obtained by using 2.3-hydroXyanthracene-carboxylic acid arylides as coupling components. Moreover, considerable advantages are involved in the production of the bluegreen tints. The new dyestuffs are well suitable for the production of prints by the known methods of base printing. In addition to blue green tints, it is also possible to produce clear orange, red, blue or other tints on the same grounding component with commercial bases, which is an advantage especially in the printing, but also in the dyeing industry. Furthermore, the new azo-dyestuffs can be produced far more economically than the dyestuffs obtained on the basis of 2.3-hydroxyanthracenecarboxylic acid arylides. These'known blue-green dyestuffs could not be introduced into practice for base printing processes, since owing to the natural color and high substantivity of the grounding component, no pure white can be produced on the unprintedparts; moreover, apart from blue-green shades, no other tints valuable for the 238 3325 Patented 1F eh. 26, 1957 industry can be produced on these grounding com ponents.

The dyestuffs of this invention, therefore, constitute a valuableenrichment of the class of ice-colors.

The 'aminoazo-compounds used as diam-components can be obtained, for example, by coupling a 'diazotized 1-amino-2.5-dialkoxy-4-nitrobenzene with an acylacetic acid arylide of the following formula I nr -co-'-crn+'co nn 'n in which R represents .an aromatic, :hydroaroinatic,

iaraliphatic or 'heterocyclic radical :and R1 represents, an

alkyl or aryl group, and subsequently reducing the nitro group to the amino group.

The following examples serve to illustrate the inven- :tion' but'they are-not intended to limit, it-thereto, the parts being by weight, unless otherwisestated:

"Example 1 3 5,6 parts of a-(4 -arninos2.5'-dimethoxybenzene-1'- azo)-acetoacetic acid anilide of the following formula of'water,thehydrochloride being formed. 1600 parts of water arethen run in,-whi1e stirring, and the mixture is diazotized at room temperature by adding dropwise, in thecourse of about 10 minutes, 17.5 parts of a sodium 'nitrite solution'of 40 percent strength. After heating to 3'OC.- 35 C.,'the diazo-soluticn is clarified by filtering on with suction. Thefiltrate is run, while stirring, intoa suspension of 1-(2".3'-hydroxynaphthoylamino)-benzene, which wasprepared as follows:

26.3 parts of 1-(2.3-hydroxynaphthoylamino)-benzene,'26 parts of alcohol vof percent strength, 13 parts of a sodium hydroxide solution of 38 B. and 40 parts of water'are stirred until dissolution is complete. The solution' is then poured into a mixture of 500 parts of water,

l0 parts of Turkey red oil and 5 parts of a sodium hydroxide solution of 38 B., and the anilide is .heated to 35 C.-40 C. and stirred for a'prolonged time atthis temperature. The precipitate is then filtered off with suction and washed well with water.

.=A;blue-green pigment dyestufl of good fa-stness to light is'obtained. It corresponds to the following formula OOHa Example 2 Well boiled and dried cotton yarn is treated for about half an hour at a ratio of goods to liquor of 1:20 in a solution (containing per liter 3 grams of l-(2. '-hydroxynaphthoylamino)-benzene, 3 grams of a formaldehyde solution of 33 percent strength, 12 cc. of a sodium hydroxide solution of 38' B6. and 10 cc. of Turkey red oil. After squeezing, the impregnated material is introduced into a developing bath which has been prepared as follows:

1.5 parts of the hydrochloride of a-(4-amino-2'.5'- diethyoxybenzene-l-azo) acetoacetic acid anilide are added, while stirring, to a mixture of 150 parts of water and 1.5 parts of hydrochloric acid of 20 perccent strength. The mixture is diazotized, by adding dropwise 1.2 parts of a sodium nitrite solution of 20 percent strength. The excess of mineral acid is neutralized by the addition of 5 parts of a sodium acetate solution of 10 percent strength, 5 parts of an acetic acid of 30 percent strength are then added and the solution of the diazoniurn salt is made up to 1000 parts.

The dyeing is developed for l520 minutes, rinsed with hot water and after-treated at the boil for half an hour with a solution containing per liter of liquor 3 grams of soap and 2 grams of anhydrous sodium carbonate. A clear blue-green dyeing of good fastness to light, good properties of wet fastness and medium fastness to chlorine is obtained.

When the same diam-compound is coupled on cotton yarn in the manner described above with 1-(2'.3' hydroxynaphthoylamino) 2 methylbenzene, a somewhat greener dyeing of similar properties is obtained.

Example 3 Staple fiber yarn of regenerated cellulose is treated for about 20-30 minutes at a ratio of goods to liquor of 1:20 in a solution containing per liter 1.5 grams of l-(6'- methoxy 2.3' hydroxynaphthoylamino) 2 methyl-4- chlorobenzene, 11 cc. of a sodium hydroxide solution of 38 B., 1.5 cc. of a formaldehyde solution of 33 percent strength and 10 cc. of Turkey red oil. After squeezing, the impregnated yarn is introduced into a developing bath containing per liter 5 grams of a dyeing salt which consists of the diazonium chloride of a-(4'-amino-2.5- dimethoxybenzene l-azo)-acetoacetic acid-3-ethoxyanilide with a content of the base of 25 percent and 2 grams of acetic acid of 50 percent strength. The dyeing is developed for 20-30 minutes, rinsed and after-treated at the boil for half an hour with a solution containing per liter of liquor 3 grams of soap and 2 grams of anhydrous sodium carbonate. A clear green dyeing of very good fastness to light and good properties of wet fastness is obtained.

In the same manner the dyestulf can be produced on viscose rayon yarn, a somewhat more intense dyeing being obtained.

Example 4 Cotton fabric is padded on the foulard with a solution containing per liter 8 grams of 1-(2.3'-hydroxynaphthoylamino)-2-methylbenzene, 15 grams of a sodium hydroxide solution of 38 B. and 15 grams of Monopol Brilliant Oil, dried and printed with a paste containing in 1000 grams 50 grams of a dyeing salt consisting of the diazonium salt of a-(4-amino-2'.5-dimethoxybenzene-l-azo) -acetoacetic acid anilide with a content of the base of 22 percent, 480 grams of water, 450 grams of starch-thragacanth thickening and 20 grams of acetic acid 01 50 percent strength. After drying, the material is passed through a boiling bath containing per liter 10 grams of anhydrous sodium carbonate, rinsed and after-treated at the boil for some minutes with a solution containing 3 grams of soap and 2 grams of sodium carbonate per liter of liquor. An intense blue-green print of good fastness to light and good properties of wet fastness is obtained.

The above printing process can also be applied to other kinds of fabric, for example staple rayon or viscose rayon crepe.

4 When other diazotized aminoazo-compounds of the above constitution and other 2.3-hydroxynaphthoic acid arylides are used according to the usual dyeing or printing processes, dyestulfs of similar good fastness proper- 5 ties are obtained.

The following table indicates the tints obtained by subectmg the material to an after-treatment with a boiling solution of soap and sodium carbonate:

Dinzo component Coupling component Tint dlmethxybenzene-lthoylnmlno) 15 azo)-acetoaeetie acid (1) -anilido -benzene blue-green. (2) -anillde. -2-methyl-4-ehloroben- Do.

zene.

(3) -anilide -2-methyl-4 -methoxygreenish-blue.

benzene.

(4) -anlllde -2.4 dimethoxy 5 ehloblue-green.

20 robenzene.

(5) -anllitle -naphthalene Do.

(6) -2-methyl-anilido...- -2-metbylbenzene. Do.

(8) -3-methyl-anilide -2-methylbenzene.. Do.

(9) -3-methyl'nnilide 2 methyl 4 chloroben- D0.

(10) -4-methyl-ani1ide. -benzene Do.

25 (11) -4-methyl-anilide c -2-methylbenzene Do.

(12) -4-methy1-anilide.-. -2-methyl-4-chlorobengreenlsh-blue.

(13) -3-chloro-anilide greenblue. (14) -3-ehlero-anilid blue-green. (15) -3-ehloro-anillde. greenlsh'bluo.

benzene.

30 (16) -4-chloro-anllide -benzene blue-green.

(17) -4-chloro-anilide. -2-meth,vlbenzene. D0.

(18) -4-chloro anilide. -2-methoxybenzene Do.

(19) -3-ethoxy-anilide.. -benzene Do.

(20) -3-ethoxy-anilide -2-methylbenzene Do.

(21) -3-ethoxy-snilide -2-methy1-4-chlorobem green.

zene.

(22) '3-othoxy-anilide -2-methoxybenzene bluegreen.

35 (23) -4-ethoxy-anilide -benzene green.

(24) -4-eth0xy-anilide. -2-methylbenzene D0.

(25) -2.3-dimeth vl-anilide. -benzene blue-green.

(26) -2.3-dimethyl-anilide. -2-methylbenzeno green.

(27) -2.3-dimethy1-anilide. 2b methyl 4 chlorogreenlsh blue.

enzene.

(2S) -2.4-dimethyl-anilide -benzene blue-green.

4 (29) -2.4-dimethyl-anilide -2-methylbenze Do.

(30) -2.5-dimethyl-anilide -benzene dull blue-green. (31) -2.5-dimethyl'anillde -2-methylbenzene. green.

(32) 2 methyl 4 -benzene greenish-blue.

chloro-anilide.

(33)-- 2 ethylsulionyldo blue.

5 trifluoromethyl anilide.

45 (34) 2 ethylsultonyl- -2-methylbenzcne Do.

5 trifluoromethyl anilide.

(35) -2.5-dichloro-amdo Do.

(36) diphenylsullone 2 methyl 4 chloroblue-green.

Z-amide. benzene.

(37) cyelohexyl 1 -benzene grey-blue.

5O amide.

(38) -naphthyl-l-amide. -2-methylbenzene grey-green.

(39) -nnphthyl-2-nmide -benzene blue-green.

(41) -nephthyl2-amide. 2 methyl 4 ehloro blue-green. benzene.

(42) -anthraquinonyl-2- -benzene grey-green.

55 amide.

(43) -6-methoxybenzthido grey-blue.

azole-2-arnide.

(44) -6-methoxybenz- 2 -rnethyl 4 ehlorodark blue.

thlazole-2-amidc. benzene.

(45) N ethyl cerbaz- -benzene blue-green.

oly1-3-amide.

(46) N ethyl carbaz- -2'methy1benzeno- Do.

60 olyl-3-amldo.

a-(4-amln0-2' .5 -d1ethoxybenzene-1 -azo)-acetoacetic acid (47) -anillde -2-methoxybenzene D0. (48) -anilide. naphthalene green. 05 (49) -anilide 2 (2 .3 hydroxynaphdark green.

thoylnmino) naphthalene.

1-(2 .3-hydr0xynaphthoylamino) 70 (50) -3-methyl-anlllde -benzene blue'green.

(51) -3-methyl-anilide -2-methylbenzene. Do. (52) -3-methyl-anllide 2 methyl 4 chloro-ben- Do.

zene. (53) -3-methyl-anillde maphthalene green. (54) -benzylamlde -benzene blue. (55) -benzylamide -naphthnlene greenish-blue. (56) -2-ehloro-anillde. -2-methylbenzene. blue-green. 7 (57) 4-chlot'o'anilidenu -benzene blue-grcen.

Coupling component Tint Dlazo component (58) -4-chloro-anilide. -2-metl1ylbenzene blue-green. 0 CH: O (3 H;

5 -dlmethoxybenzene-1 -azo)-benz0ylacet1e acid 0 (69) -anllide -benzene greenish-blue. 0 CH; A} (60) -nnillde -2-methylbenzene Do. H; o (61) -an1llde -2-methyl-4-ohl0ro-benblue. 0H

zene. m a-(4'-amlno-2' .5'-d1- 1-(6'-bromo-2 .3'- H100 CO-NHO-Cl methoxybenzened hydroxynaphthoylamino) -nzo)-acetoacetlc acid 6H (62) enillde -benzene bluegreen.

5. The water-insoluble azo-dyestufi corresponding to the following formula I claim: I 1. The water-insoluble azo-dyestufis corresponding to the following general formula 0 Oalkyl N= N=NCHCO--NH 1 N= N=N-0H-CO-NH-R cm (5 81m on R1 0H (JO-NH x (JO-NH-Rz HI 6. The water-insoluble azo-dyestuff corresponding to wherein R represents a member of the group consisting 0 the following formula of radicals of the benzene and naphthalene series, an

anthraquinonyl, a cyclohexyl, benzyl, benzthiazole and car- 3 bazole radical, R1 represents a member of the group con- OCH! OOIHE sisting of methyl and phenyl, R2 represents a member of the group consisting of radicals of the benzene and naph- N=N thalene series, and X stands for a member of the group do consisting of hydrogen, methoxy and bromine. 0 H

2. The water-insoluble azo-dyestuffs corresponding to 011 the following general formula (mm 7 00-NH 01 m N=N N=N-oH-oo-NH-R 1 o 7. The water-insoluble azo-dyestufi corresponding to the following formula I OH 5 OCIH; x O0NHR N=NON=N.CH CO NH wherein R represents a radical of the benzene series, R: J represents a member of the group consisting of radicals of 5 the benzene and naphthalene series, and X stands for a OH member of the group consisting of hydrogen, methoxy and bromine. (JO-NH 3. The water-insoluble azo-dyestufi corresponding to the following formula N=N ketelencel in the file Of Patent C'Hi 490 UNITED STATES PATENTS OH 0 2,069,158 Schnitzspahn et al. Jan. 26, 1937 2,112,764 Dahlen et al. Mar. 29, 1938 O 2,175,370 Zwilgmeyer Oct. 10, 1939 

1. THE WATER-INSOLUBLE AZO-DYESTUFFS CORRESPONDING TO THE FOLLOWING GENERAL FORMULA 